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WO2015141151A1 - Solution for forming function layer contained in organic light emitting element and method for manufacturing organic light emitting element - Google Patents

Solution for forming function layer contained in organic light emitting element and method for manufacturing organic light emitting element Download PDF

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Publication number
WO2015141151A1
WO2015141151A1 PCT/JP2015/001002 JP2015001002W WO2015141151A1 WO 2015141151 A1 WO2015141151 A1 WO 2015141151A1 JP 2015001002 W JP2015001002 W JP 2015001002W WO 2015141151 A1 WO2015141151 A1 WO 2015141151A1
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solvent
solution
boiling point
viscosity
organic light
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French (fr)
Japanese (ja)
Inventor
高田 昌和
裕隆 南野
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Joled Inc
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Joled Inc
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Priority to US15/125,403 priority Critical patent/US9865816B2/en
Priority to JP2016508493A priority patent/JP6317429B2/en
Publication of WO2015141151A1 publication Critical patent/WO2015141151A1/en
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10Deposition of organic active material
    • H10K71/12Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14Carrier transporting layers
    • H10K50/15Hole transporting layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14Carrier transporting layers
    • H10K50/16Electron transporting layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00Properties of the organic materials covered by group H10K85/00
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00Properties of the organic materials covered by group H10K85/00
    • H10K2101/20Delayed fluorescence emission

Definitions

  • the present invention relates to physical properties of a solution for forming a functional layer included in an organic light emitting device.
  • An organic light-emitting element is a light-emitting element using an electroluminescence phenomenon of an organic material, and includes a pair of electrodes composed of an anode and a cathode, and a light-emitting layer sandwiched between the electrodes.
  • a hole injection layer, a hole transport layer, or a hole injection / transport layer is interposed between the anode and the light emitting layer, and between the cathode and the light emitting layer, if necessary.
  • An electron injection layer, an electron transport layer, or an electron injection / transport layer is interposed.
  • the light emitting layer, hole injection layer, hole transport layer, hole injection / transport layer, electron injection layer, electron transport layer, and electron injection / transport layer each perform their own functions such as light emission, charge injection and transport. These layers are collectively referred to as “functional layers”.
  • organic light emitting elements correspond to RGB sub-pixels, and adjacent RGB sub-pixels are combined to form one pixel, and the pixels are arranged in a matrix. An image display area is formed.
  • the length of one side of each pixel is required to be formed with a minute size of about 500 ⁇ m or less.
  • the thickness of the functional layer in each element needs to be set as thin as several tens to several hundreds nm.
  • the light emitting characteristics of the organic light emitting element are sensitive to the film thickness of the functional layer, it is required to form the functional layer flat when the functional layer is formed by a wet method.
  • the film thickness at the end of the functional layer becomes thicker than the film thickness at the central part, or the film thickness at the end of the functional layer becomes thinner than the film thickness at the central part. In some cases, it is difficult to ensure the flatness of the functional layer.
  • an object of the present invention is to provide a solution capable of reducing a difference in film thickness between an end portion and a central portion of a functional layer, and a method for manufacturing an organic light emitting element.
  • the solution according to one embodiment of the present invention is a solution for forming a functional layer included in the organic light emitting element.
  • the solution includes a functional material constituting the functional layer and a solvent.
  • the solvent includes a high boiling point solvent composed of one or more solvent components having a boiling point of 200 ° C. or higher.
  • the high boiling point solvent has a viscosity of 13 mPa ⁇ s to 25 mPa ⁇ s and a surface tension of 33 mN / m to 37 mN / m.
  • (A)-(c) is a schematic diagram showing a drying process of a solution when a functional layer is formed by a wet method. Diagram showing boiling point, vapor pressure, viscosity and surface tension of each solvent component (A) is a plan view of the substrate used in the experiment, and (b) is a cross-sectional view taken along the line AA.
  • (A) is a schematic diagram when the shape of the functional layer is flat
  • (b) is a schematic diagram when the shape of the functional layer is convex
  • (c) is a diagram when the shape of the functional layer is concave.
  • Pattern diagram The figure which shows an example of the photograph of the functional layer formed using each solvent, and the evaluation result of the shape of the functional layer Figure showing the results of evaluating the shape of the functional layer, the viscosity of the high boiling point solvent in the solution, and the surface tension of the high boiling point solvent in the solution A graph plotting the viscosity of the high boiling point solvent and the surface tension of the high boiling point solvent for each solvent
  • the figure which shows the plane shape and cross-sectional shape of the functional layer for every solvent A graph plotting the ratio of the high-viscosity solvent occupying the high-boiling solvent of each solvent and the flat area of the flat area in the light-emitting area Graph showing the dependence of functional material concentration in solution on solution viscosity FIGS.
  • FIG. 4A to 4G are cross-sectional views for explaining a method for manufacturing an organic light-emitting element.
  • the perspective view which shows an example of the shape of a partition layer The perspective view which shows another example of the shape of a partition layer (A)-(c) is a schematic diagram showing the drying process of the solution when the partition layer of FIG. 13 is used.
  • Functional block diagram of organic display device A perspective view illustrating the appearance of an organic display device
  • FIG. 1 shows a drying process of a solution when a functional layer is formed by a wet method.
  • the solution 13 includes a functional material constituting the functional layer and a solvent for dissolving or dispersing the functional material.
  • the solution 13 is applied to the region partitioned by the partition wall 12 on the substrate 11 (FIG. 1A).
  • the applied solution 13 has a shape in which the central portion swells due to the surface tension of the solution 13.
  • the solvent in the solution 13 gradually evaporates from the surface of the solution 13.
  • the evaporation rate of the solvent at the end of the solution 13 is larger than the evaporation rate of the solvent at the center. This is because the evaporated solvent is difficult to escape over the central part and the vapor pressure of the solvent is easily maintained high, whereas the evaporated solvent easily escapes to the surroundings and tends to lower the solvent vapor pressure over the edge.
  • a solution flow 14 is generated in the direction from the central portion to the end portion in the surface layer portion of the solution 13, and accordingly, in the deep layer portion of the solution 13, the solution flows in the direction from the end portion to the central portion.
  • Stream 15 is generated.
  • the amount of the solution 13 gradually decreases (FIG. 1B), and the concentration of the functional material increases accordingly.
  • all the solvent in the solution 13 evaporates to form the functional layer 16 made of a functional material (FIG. 1C).
  • the shape of the functional layer 16 is more dependent on the shape of the solution at the end (FIG. 1 (b)) and the behavior of the functional material in the solution than at the beginning of the drying process of the solution 13 (FIG. 1 (a)). Conceivable.
  • the inventors appropriately set parameters that determine the shape of the solution 13 and the behavior of the functional material at the end of the drying process of the solution 13 in order to reduce the film thickness difference between the end and the center of the functional layer 16. I thought it should be adjusted. Furthermore, the inventors paid attention to the viscosity and surface tension of a high-boiling solvent having a boiling point of 200 ° C. or higher as these parameters.
  • the high boiling point solvent is focused on because the physical properties of the solution 13 at the end of the drying process of the solution are considered to largely depend on the physical properties of the high boiling point solvent.
  • the solution 13 includes a high-boiling solvent and a low-boiling solvent
  • the low-boiling solvent evaporates before the high-boiling solvent in the drying process of the solution 13, and a large amount of the high-boiling solvent remains at the end of the drying process of the solution 13. Will do.
  • the solution 13 includes a high boiling point solvent and does not include a low boiling point solvent, only the high boiling point solvent exists at the beginning and the end of the drying process of the solution 13.
  • the solution 13 contains a high boiling point solvent
  • the physical properties of the solution 13 at the end of the drying process of the solution 13 largely depend on the physical properties of the high boiling point solvent.
  • the reason for focusing on viscosity and surface tension among the physical properties of high-boiling solvents is that viscosity affects the behavior of functional materials in solution, and surface tension is thought to affect the shape of the solution. is there.
  • the inventors selected one or a plurality of solvent components, and obtained a plurality of solvents by mixing the selected solvent components in one or a plurality of volume ratios. And the functional layer 16 was formed using each solvent, and the shape of each functional layer 16 was observed. As a result, it has been found that if the viscosity and surface tension of the high-boiling solvent contained in the solution are within a specific range, the film thickness difference between the end portion and the central portion of the functional layer 16 can be reduced.
  • a solution according to one aspect of the present invention includes a functional material that constitutes a functional layer included in an organic light-emitting element, and a solvent.
  • the solvent includes a high boiling point solvent composed of one or more solvent components having a boiling point of 200 ° C. or higher.
  • the high boiling point solvent has a viscosity of 13 mPa ⁇ s to 25 mPa ⁇ s and a surface tension of 33 mN / m to 37 mN / m.
  • the viscosity of the high boiling point solvent was calculated by calculating the product of the volume ratio of the solvent component and the viscosity of the solvent component at room temperature for each solvent component. It is obtained by adding the product of each solvent component.
  • the surface tension of the high boiling point solvent is obtained by calculating the product of the volume ratio of the solvent component and the surface tension of the solvent component at room temperature for each solvent component, and adding the calculated product of each solvent component. It is done.
  • the viscosity of the high boiling point solvent may be greater than 15 mPa ⁇ s.
  • At least one of the one or more solvent components constituting the high boiling point solvent is a high viscosity solvent having a viscosity of 20 mPa ⁇ s or more, and the proportion of the high viscosity solvent in the high boiling point solvent is 35 vol% or more. It is good as well. Thereby, the ratio of the flat area
  • the ratio of the high viscosity solvent to the high boiling point solvent may be 50 vol% or more. Thereby, the ratio of the flat area
  • the solvent may further include a low boiling point solvent composed of one or a plurality of solvent components having a boiling point of less than 200 ° C.
  • the viscosity of the solution may be 5 mPa ⁇ s or more and 15 mPa ⁇ s or less.
  • the viscosity of the solution has an appropriate range from the viewpoint of ease of application.
  • the viscosity of the high-boiling solvent is determined from the viewpoint of the flatness of the shape of the functional layer, and thus the viscosity of the solution may deviate from a range suitable for application. Therefore, the viscosity of the solution may be adjusted to an appropriate range by including a low boiling point solvent in the solution.
  • one or more solvent components constituting the low boiling point solvent may have a boiling point higher than 160 ° C. As a result, it is possible to prevent a situation in which a part of the low boiling point solvent evaporates before application of the solution and the concentration of the solution and the solvent composition ratio change.
  • the solvent may further include a low-boiling solvent composed of one or more solvent components having a boiling point of less than 200 ° C., and the proportion of the high-boiling solvent in the solvent may be 80% or less.
  • the proportion of the high boiling point solvent in the solvent may be 60% or less.
  • the method for manufacturing an organic light-emitting element of one embodiment of the present invention functions by forming a first electrode, applying a solution containing a functional material and a solvent above the first electrode, and drying the applied solution.
  • a functional layer made of a functional material is formed above the first electrode, and a second electrode is formed above the functional layer.
  • the solvent includes a high boiling point solvent composed of one or a plurality of solvent components having a boiling point of 200 ° C. or higher.
  • the high boiling point solvent has a viscosity of 13 mPa ⁇ s to 25 mPa ⁇ s and a surface tension of 33 mN / m to 37 mN / m.
  • the film thickness difference between the end portion and the central portion of the functional layer can be reduced, and as a result, good light emission characteristics of the organic light emitting device can be obtained.
  • the solution contains a functional material.
  • the functional material is a material constituting the functional layer included in the organic light emitting element.
  • the functional layer is, for example, a light emitting layer, a hole injection layer, a hole transport layer, a hole injection / transport layer, an electron injection layer, an electron transport layer, and an electron injection / transport layer.
  • Examples of the material for the hole injection layer, the hole transport layer, and the hole injection / transport layer include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives described in Patent Document 2, phenylenediamine Derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, polyphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds, butadiene compounds, polystyrene derivatives, hydrazone derivatives , Triphenylmethane derivatives, and tetraphenylbenzine derivatives.
  • Examples of the material for the light emitting layer include the oxinoid compound, perylene compound, coumarin compound, azacoumarin compound, oxazole compound, oxadiazole compound, perinone compound, pyrrolopyrrole compound, naphthalene compound, anthracene compound, and fluorene compound described in Patent Document 2.
  • Examples of the material for the electron injection layer, the electron transport layer, and the electron injection / transport layer include, for example, a nitro-substituted fluorenone derivative, a thiopyrandioxide derivative, a difequinone derivative, a perylenetetracarboxyl derivative, and an anthraquinodimethane derivative described in Patent Document 2.
  • Fluorenylidenemethane derivatives, anthrone derivatives, oxadiazole derivatives, perinone derivatives, and quinoline complex derivatives can be used.
  • the solution contains a solvent in addition to the functional material.
  • the solvent includes a high boiling point solvent, and optionally includes a low boiling point solvent.
  • the boundary between the high boiling point and the low boiling point is set to 200 ° C. for convenience.
  • the high boiling point solvent is composed of one or more solvent components having a boiling point of 200 ° C. or higher.
  • the low boiling point solvent is composed of one or more solvent components having a boiling point of less than 200 ° C.
  • At least one of one or a plurality of solvent components constituting the high boiling point solvent is used as a high viscosity solvent.
  • the boundary between high viscosity and low viscosity is 20 mPa ⁇ s.
  • the solvent component examples include methanol, ethanol, propanol, isopropyl alcohol, butanol, butanol, isobutyl alcohol, and sec-butyl alcohol.
  • Tert-butyl alcohol Tert-Butyl Alcohol
  • ethylene glycol Ethylene Glycol
  • 1,2-dimethoxyethane diethyl ether
  • Diethyl Ether diisopropyl ether
  • acetic acid Acetic Acid, Ethyl ⁇ ⁇ Acetate
  • Acetic anhydride Acetic Anhydride
  • Tetrahydrofuran 1,4-Dioxane
  • Acetone Ethyl methyl ketone
  • Carbon tetrachloride Chloroform Dichloromethane, 1,2-Dichloroethane, Benzene, Toluene, Xylene, Cyclohexane, Pentane,
  • the inventors prepared the solvent shown in FIG. 2 as the solvent component.
  • FIG. 2 shows the boiling point, vapor pressure, viscosity, and surface tension of each solvent component.
  • the inventors select one or a plurality of solvent components from among these solvent components, and mix the selected solvent components at an appropriate volume ratio, so that the solvents A, B, C, D, E, F, G and H were obtained.
  • FIG. 3A shows a plan view of the substrate used in the experiment
  • FIG. 3B shows a cross-sectional view taken along the line AA.
  • the partition wall 12 surrounds a region where the functional layer of the glass substrate 11 is formed.
  • the width in the longitudinal direction of the region partitioned by the partition 12 is about 254 ⁇ m, and the width in the short direction is about 60 ⁇ m.
  • the target film thickness of the functional layer 16 is set to 30 nm.
  • the inventors further classified the shape of the formed functional layer into “flat”, “convex” or “concave”.
  • a method for classifying the shape of the functional layer will be described with reference to FIG. 4A shows flatness, FIG. 4B shows a convex shape, and FIG. 4C shows a concave shape.
  • the position where the height of the upper surface of the functional layer 16 from the substrate 11 is 200 nm is defined as the reference position.
  • the reference position In the cross section of FIG. 4A, there are two reference positions. The region sandwiched between these reference positions is defined as the light emitting region of the functional layer 16. The position of the center of the light emitting region of the functional layer 16 is defined as the central portion C of the functional layer 16. Further, the positions near the central portion C by 12.5% of the width of the light emitting region of the functional layer 16 from the respective reference positions are defined as the end portion L and the end portion R of the functional layer 16, respectively.
  • the thickness of the central portion C of the functional layer 16 is d C
  • the thickness of the end portion L is d L
  • the thickness of the end portion R is d R.
  • ⁇ d is calculated using the following formula, and the shape of the functional layer 16 is classified using the film thickness difference ⁇ d.
  • ⁇ d (d L + d R ) / 2 ⁇ d C “Flat” means that the absolute value of the film thickness difference ⁇ d is 20% or less of the film thickness d C of the central portion C.
  • the “convex shape” is a case where the absolute value of the film thickness difference ⁇ d is larger than 20% of the film thickness d C of the central portion C and the film thickness difference ⁇ d is negative.
  • the “concave shape” is a case where the absolute value of the film thickness difference ⁇ d is larger than 20% of the film thickness d C of the central portion C and the film thickness difference ⁇ d is positive.
  • FIG. 5 shows an example of a photograph of a functional layer formed using each solvent and an evaluation result of the shape of the functional layer.
  • FIG. 6 shows the evaluation results of the shape of the functional layer, the viscosity of the high boiling point solvent in the solution, and the surface tension of the high boiling point solvent in the solution.
  • FIG. 7 shows the viscosity of the high boiling point solvent and the high boiling point solvent in each solvent. The graph which plotted surface tension is shown.
  • the shape of the functional layer became flat. From this, in order to flatten the shape of the functional layer, the viscosity of the high boiling point solvent in the solution is 13 mPa ⁇ s to 25 mPa ⁇ s, and the surface tension of the high boiling point solvent in the solution is 33 mN / m to 37 mN / s. It can be seen that it should be less than m. Further, since the higher the boiling point of the solvent, the higher the tendency of the flattening, the more preferable the viscosity of the high boiling point solvent in the solution is greater than 15 mPa ⁇ s.
  • the lower limit of the surface tension range of the high boiling point solvent in the solution may be 34 mN / m instead of 33 mN / m.
  • the upper limit of the surface tension range of the high-boiling solvent in the solution may be 36 mN / m instead of 37 mN / m.
  • the viscosity of the high boiling point solvent in the solution to 25 mPa ⁇ s or less, it can be suitably used for an ink jet method.
  • FIG. 8 shows the planar shape and cross-sectional shape of the functional layer for each solvent.
  • the scale of the planar image is common to each solvent.
  • the scale of the cross-sectional image is common to each solvent. According to this, the group including the solvents D, F, and G (the shape of the functional layer is flat in FIG. 7) and the group including the solvents A, B, C, and E (the shape of the functional layer is convex or concave in FIG.
  • the shape of the functional layer is different.
  • a so-called coffee stain phenomenon occurs, and in the group including the solvents A, B, C, and E, the coffee stain phenomenon does not occur.
  • the cause of these differences is considered to be due to the proportion of the high boiling point solvent in the solvent.
  • the proportion of the high boiling point solvent is 33% for solvent A, 33% for solvent B, 60% for solvent C, 100% for solvent D, 53% for solvent E, 83% for solvent F, and 83% for solvent G. . If the ratio of the high boiling point solvent is large, convection is likely to occur during the drying process of the solution, and as a result, the coffee stain phenomenon is considered to occur.
  • the viscosity and surface tension of the high-boiling solvent are about the same as those of the group containing the solvents D, F, and G (13 mPa ⁇ s to 25 mPa ⁇ s, 33 mN / m to 37 mN / m), and higher. It is preferable to lower the boiling point solvent ratio than the group containing the solvents D, F and G (80% or less). Furthermore, it may be lowered to the same level as the solvents A, B, C and E (60% or less). Thereby, a better film shape can be obtained. In addition, the ratio of the high boiling point solvent can be easily lowered by the addition of the low boiling point solvent.
  • the inventors prepared a plurality of solvents, formed a functional layer using each solvent, and examined a ratio of a flat region in a light emitting region of the formed functional layer.
  • the flat region is the length of a region where the functional layer thickness falls within a range of ⁇ 20% from the target film thickness (30 nm in this example).
  • FIG. 9 is a graph plotting the ratio of the high-viscosity solvent occupying the high boiling point solvent of each solvent and the flat area of the flat area occupying the light-emitting area.
  • the proportion of the high-viscosity solvent is 0 vol%
  • the proportion of the flat region in the light emitting region is distributed in the range of 40% to 60%.
  • the proportion of the flat region in the light emitting region is distributed in the range of 60% to 70%.
  • the proportion of the flat region in the light emitting region is distributed in the range of 75% to 85%.
  • the solvent group in which the proportion of the high-viscosity solvent is around 35 vol% has a larger proportion of the flat region in the light emitting region than the solvent group in which the proportion of the high-viscosity solvent is 0 vol%.
  • the proportion of the flat region in the light emitting region is further large, which is about 75% to 85%. Therefore, the flatness of the functional layer can be improved by setting the proportion of the high viscosity solvent in the high boiling point solvent to 35 vol% or more.
  • the ratio of the high viscosity solvent is more preferably 50 vol% or more.
  • FIG. 10 shows the dependence of the concentration of the functional material in the solution on the viscosity of the solution.
  • Four types of solutions with different functional materials were prepared using a common solvent, and the change in the viscosity of the solution when the concentration of the functional material in the solution was varied for each solution was measured. According to this, it turns out that the viscosity of a solution becomes large, so that the density
  • the ratio of the change in the viscosity of the solution to the change in the concentration of the functional material is smaller than in the case of the high molecular material.
  • the concentration of the functional material increases as the solvent evaporates during the drying of the solution.
  • FIG. 10 shows that the viscosity of the solution increases as the concentration of the functional material increases in the course of drying the solution.
  • the viscosity of the solution is increased, the flow of the solution is weakened, and the influence on the behavior of the functional material is reduced.
  • the ratio of the change in the viscosity of the solution with respect to the change in the concentration of the functional material is smaller than in the case of the high molecular material.
  • the functional material when the functional material is a polymer material, the flow of the solution tends to be weak, and the influence on the behavior of the functional material is small.
  • the functional material when the functional material is a low molecular material, the flow of the solution is difficult to weaken, and the influence on the behavior of the functional material is great. In other words, it can be said that flattening the shape of the functional layer is difficult when the functional material is a high molecular material or a low molecular material, but is particularly difficult when the functional material is a low molecular material.
  • the low molecular weight material refers to a material for which the Mark-Houwink-Sakurada equation does not hold. The molecular weight is several thousand or less.
  • FIG. 11 is a cross-sectional view for explaining a method for manufacturing an organic light emitting device.
  • the substrate 101 is prepared, and the first electrode 102 is formed on the substrate 101 (FIG. 11A).
  • the partition layer 103 is formed on the substrate 101 (FIG. 11B).
  • the partition layer 103 is electrically insulating and has an opening above the first electrode 102. A portion around the opening of the partition layer 103 functions as a partition.
  • FIG. 12 shows the shape of the partition wall layer 103.
  • the solution 104 is applied to the region partitioned by the partition layer 103 above the first electrode.
  • the solution 104 includes a functional material and a solvent.
  • the functional material will be described as a material for forming the hole injection / transport layer.
  • the solvent includes a high boiling point solvent composed of one or more solvent components having a boiling point of 200 ° C. or higher.
  • the high boiling point solvent has a viscosity of 13 mPa ⁇ s to 25 mPa ⁇ s and a surface tension of 33 mN / m to 37 mN / m.
  • the applied solution 104 is dried to form a hole injection / transport layer 105 above the first electrode 102 (FIG. 11D). Drying is performed at atmospheric pressure or in vacuum, with or without heating.
  • the light emitting layer 106 is formed above the hole injection / transport layer 105 (FIG. 11E), and the electron injection / transport layer 107 is formed above the light emitting layer 106 (FIG. 11F).
  • a second electrode 108 is formed above the injection / transport layer 107 (FIG. 11G).
  • the difference in film thickness between the end portion and the central portion of the hole injection / transport layer 105 can be reduced, and as a result, good light emission characteristics of the organic light emitting device can be obtained.
  • the solvent may have other features disclosed in the first embodiment in addition to the above features.
  • the viscosity of the high boiling point solvent may be greater than 15 mPa ⁇ s.
  • the ratio of the high viscosity solvent to the high boiling point solvent may be 35 vol% or more, or 50 vol% or more.
  • the solvent may include a low boiling point solvent composed of one or a plurality of solvent components having a boiling point of less than 200 ° C., and the viscosity of the solution may be 5 mPa ⁇ s or more and 15 mPa ⁇ s or less. By setting the viscosity of the solution within this range, it can be suitably used for an ink jet method.
  • One or more solvent components constituting the low boiling point solvent may all have a boiling point higher than 160 ° C. As a result, it is possible to prevent a situation in which a part of the low boiling point solvent evaporates before application of the solution and the concentration of the solution and the solvent composition ratio change.
  • the hole injection / transport layer 105 is illustrated as a functional layer formed by application of a solution, but is not limited thereto.
  • the hole injection / transport layer 105 the light emitting layer 106 or the electron injection / transport layer 107 may be formed by application of a solution.
  • several of these functional layers may be formed by application
  • the first electrode, the hole injection / transport layer, the light emitting layer, the electron injection / transport layer, and the second electrode are stacked, but the present invention is not limited to this.
  • the partition wall layer 103 has the shape shown in FIG. 12, but the present invention is not limited to this.
  • a partition wall layer 203 having a shape shown in FIG. 13 may be used.
  • the partition layer 203 includes a plurality of first banks 203a and a plurality of second banks 203b.
  • the first bank 203a is along the longitudinal direction of the light emitting region.
  • the second bank 203b exists between the adjacent first banks 203a and extends along the short direction of the light emitting region.
  • the height of the second bank 203b is lower than the height of the first bank 203a.
  • FIG. 14 shows a drying process of the solution when the partition wall layer of FIG. 13 is used.
  • partition region a region partitioned by the partition layer 203
  • the solution 204 applied to a region partitioned by the partition layer 203 reaches the adjacent partition region beyond the second bank 203b (FIG. 14 (a)).
  • the solution 204 is accommodated in the partition region (FIG. 14B), and after further drying, the functional layer 205 is formed in the partition region above the first electrode 102.
  • the final stage of the drying process of the solution 204 (FIG. 14B) is the same situation as when the partition wall layer 103 is used. Therefore, even when the partition wall layer 203 is used, the same effect as when the partition wall layer 103 is used can be obtained.
  • FIG. 15 shows functional blocks of the organic display device.
  • FIG. 16 illustrates the appearance of the organic display device.
  • the organic display device 20 includes an organic display panel 21 and a drive control unit 22 electrically connected thereto.
  • the organic display panel 21 has the organic light emitting element shown in FIG.
  • the drive control unit 22 includes a drive circuit 23 that applies a voltage between the first electrode 102 and the second electrode 108, and a control circuit 24 that controls the operation of the drive circuit 23.
  • One embodiment of the present invention can be used for, for example, an organic light-emitting element.

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Abstract

This solution contains a solvent and a functional material that constitutes a function layer. The solvent contains a high-boiling-point solvent that is composed of one or more solvent components having a boiling point of 200°C or more. The high-boiling-point solvent has a viscosity of from 13 mPa·s to 25 mPa·s (inclusive) and a surface tension of from 33 mN/m to 37 mN/m (inclusive).

Description

有機発光素子に含まれる機能層を形成するための溶液、および、有機発光素子の製造方法Solution for forming functional layer contained in organic light emitting device, and method for manufacturing organic light emitting device

 本発明は、有機発光素子に含まれる機能層を形成するための溶液の物性に関する。 The present invention relates to physical properties of a solution for forming a functional layer included in an organic light emitting device.

 近年、有機発光素子の研究開発が進んでいる。有機発光素子は、有機材料の電界発光現象を利用した発光素子であり、陽極と陰極とからなる一対の電極と、電極間に挟まれた発光層とを有する。また、陽極と発光層との間には、例えば、必要に応じてホール注入層、ホール輸送層またはホール注入兼輸送層が介挿され、陰極と発光層との間には、必要に応じて電子注入層、電子輸送層または電子注入兼輸送層が介挿される。発光層、ホール注入層、ホール輸送層、ホール注入兼輸送層、電子注入層、電子輸送層、および電子注入兼輸送層は、各々発光、電荷の注入と輸送といった固有の機能を果たすので、これらの層を総称して「機能層」と称する。 In recent years, research and development of organic light-emitting elements has progressed. An organic light-emitting element is a light-emitting element using an electroluminescence phenomenon of an organic material, and includes a pair of electrodes composed of an anode and a cathode, and a light-emitting layer sandwiched between the electrodes. In addition, for example, a hole injection layer, a hole transport layer, or a hole injection / transport layer is interposed between the anode and the light emitting layer, and between the cathode and the light emitting layer, if necessary. An electron injection layer, an electron transport layer, or an electron injection / transport layer is interposed. The light emitting layer, hole injection layer, hole transport layer, hole injection / transport layer, electron injection layer, electron transport layer, and electron injection / transport layer each perform their own functions such as light emission, charge injection and transport. These layers are collectively referred to as “functional layers”.

 フルカラー表示の有機表示装置においては、このような有機発光素子が、RGB各色のサブピクセルに相当し、隣り合うRGBのサブピクセルが合わさって一画素が形成され、この画素がマトリックス状に配列されて画像表示領域が形成されている。 In an organic display device for full color display, such organic light emitting elements correspond to RGB sub-pixels, and adjacent RGB sub-pixels are combined to form one pixel, and the pixels are arranged in a matrix. An image display area is formed.

 このような有機表示装置において、高精細な画像を得るために、各画素の一辺の長さを500μm程度以下の微小サイズで形成することが要請されている。このように画素サイズが微小のものでは各素子における機能層の膜厚も数十~数百nmと薄く設定する必要がある。 In such an organic display device, in order to obtain a high-definition image, the length of one side of each pixel is required to be formed with a minute size of about 500 μm or less. When the pixel size is small as described above, the thickness of the functional layer in each element needs to be set as thin as several tens to several hundreds nm.

 そして、有機表示装置を製造する際には、電極の上方に機能層を形成する工程がある。この工程において、機能性材料と溶媒とを含む溶液を電極の上方に塗布し、塗布された溶液を乾燥させることにより機能層を形成するウェット方式が提案されている。 And when manufacturing an organic display device, there is a step of forming a functional layer above the electrodes. In this process, a wet method has been proposed in which a functional layer is formed by applying a solution containing a functional material and a solvent over an electrode and drying the applied solution.

日本国特開2011-23668号公報Japanese Unexamined Patent Publication No. 2011-23668 日本国特開平5-163488号公報Japanese Laid-Open Patent Publication No. 5-163488

 ところで、有機発光素子の発光特性は、機能層の膜厚に敏感であるため、機能層をウェット方式で形成する際には、機能層を平坦に形成することが要求される。しかしながら、ウェット方式で機能層を形成すると、機能層の端部の膜厚が中央部の膜厚よりも厚くなる、あるいは、機能層の端部の膜厚が中央部の膜厚よりも薄くなり、機能層の平坦性を確保しにくい場合がある。 Incidentally, since the light emitting characteristics of the organic light emitting element are sensitive to the film thickness of the functional layer, it is required to form the functional layer flat when the functional layer is formed by a wet method. However, when the functional layer is formed by the wet method, the film thickness at the end of the functional layer becomes thicker than the film thickness at the central part, or the film thickness at the end of the functional layer becomes thinner than the film thickness at the central part. In some cases, it is difficult to ensure the flatness of the functional layer.

 本発明は、上記課題に鑑み、機能層の端部と中央部の膜厚差を低減できる溶液、および、有機発光素子の製造方法を提供することを目的とする。 In view of the above problems, an object of the present invention is to provide a solution capable of reducing a difference in film thickness between an end portion and a central portion of a functional layer, and a method for manufacturing an organic light emitting element.

 本発明の一態様に係る溶液は、有機発光素子に含まれる機能層を形成するための溶液である。溶液は、機能層を構成する機能性材料と、溶媒とを含む。溶媒は、200℃以上の沸点を有する1または複数の溶媒成分から構成される高沸点溶媒を含む。高沸点溶媒は、13mPa・s以上25mPa・s以下の粘度と、33mN/m以上37mN/m以下の表面張力とを有する。 The solution according to one embodiment of the present invention is a solution for forming a functional layer included in the organic light emitting element. The solution includes a functional material constituting the functional layer and a solvent. The solvent includes a high boiling point solvent composed of one or more solvent components having a boiling point of 200 ° C. or higher. The high boiling point solvent has a viscosity of 13 mPa · s to 25 mPa · s and a surface tension of 33 mN / m to 37 mN / m.

 溶液中の高沸点溶媒の粘度と表面張力を上記範囲内とすることで、機能層の端部と中央部の膜厚差を低減することができる。 When the viscosity and surface tension of the high boiling point solvent in the solution are within the above ranges, the difference in film thickness between the end and the center of the functional layer can be reduced.

(a)~(c)は、ウェット方式で機能層を形成した場合の溶液の乾燥過程を示す模式図(A)-(c) is a schematic diagram showing a drying process of a solution when a functional layer is formed by a wet method. 各溶媒成分の沸点、蒸気圧、粘度、表面張力を示す図Diagram showing boiling point, vapor pressure, viscosity and surface tension of each solvent component (a)は実験に用いた基板の平面図であり、(b)はそのA-A断面図(A) is a plan view of the substrate used in the experiment, and (b) is a cross-sectional view taken along the line AA. (a)は機能層の形状が平坦の場合の模式図であり、(b)は機能層の形状が凸状の場合の模式図であり、(c)は機能層の形状が凹状の場合の模式図(A) is a schematic diagram when the shape of the functional layer is flat, (b) is a schematic diagram when the shape of the functional layer is convex, and (c) is a diagram when the shape of the functional layer is concave. Pattern diagram 各溶媒を用いて形成した機能層の写真の一例と機能層の形状の評価結果を示す図The figure which shows an example of the photograph of the functional layer formed using each solvent, and the evaluation result of the shape of the functional layer 機能層の形状の評価結果、溶液中の高沸点溶媒の粘度、溶液中の高沸点溶媒の表面張力を示す図Figure showing the results of evaluating the shape of the functional layer, the viscosity of the high boiling point solvent in the solution, and the surface tension of the high boiling point solvent in the solution 各溶媒の高沸点溶媒の粘度と高沸点溶媒の表面張力をプロットしたグラフA graph plotting the viscosity of the high boiling point solvent and the surface tension of the high boiling point solvent for each solvent 溶媒毎の機能層の平面形状と断面形状とを示す図The figure which shows the plane shape and cross-sectional shape of the functional layer for every solvent 各溶媒の高沸点溶媒に占める高粘度溶媒と、発光領域に占める平坦領域の平坦領域の割合をプロットしたグラフA graph plotting the ratio of the high-viscosity solvent occupying the high-boiling solvent of each solvent and the flat area of the flat area in the light-emitting area 溶液の粘度における溶液中の機能性材料の濃度の依存性を示すグラフGraph showing the dependence of functional material concentration in solution on solution viscosity (a)から(g)は、有機発光素子の製造方法を説明するための断面図FIGS. 4A to 4G are cross-sectional views for explaining a method for manufacturing an organic light-emitting element. 隔壁層の形状の一例を示す斜視図The perspective view which shows an example of the shape of a partition layer 隔壁層の形状の別の例を示す斜視図The perspective view which shows another example of the shape of a partition layer (a)~(c)は、図13の隔壁層を利用した場合の溶液の乾燥過程を示す模式図(A)-(c) is a schematic diagram showing the drying process of the solution when the partition layer of FIG. 13 is used. 有機表示装置の機能ブロック図Functional block diagram of organic display device 有機表示装置の外観を例示する斜視図A perspective view illustrating the appearance of an organic display device

 <1> 本発明の一態様に至った経緯
 図1に、ウェット方式で機能層を形成した場合の溶液の乾燥過程を示す。溶液13は、機能層を構成する機能性材料と、機能性材料を溶解または分散するための溶媒とを含む。溶液13は、基板11上の隔壁12で区画された領域に塗布される(図1(a))。
<1> Background of Achievement of One Embodiment of the Invention FIG. 1 shows a drying process of a solution when a functional layer is formed by a wet method. The solution 13 includes a functional material constituting the functional layer and a solvent for dissolving or dispersing the functional material. The solution 13 is applied to the region partitioned by the partition wall 12 on the substrate 11 (FIG. 1A).

 塗布された溶液13は、溶液13の表面張力により中央部が膨らんだ形状となる。溶液13中の溶媒は、溶液13の表面から次第に蒸発する。このとき、図1(a)に示すように、溶液13の端部の溶媒の蒸発速度が中央部の溶媒の蒸発速度よりも大きい。これは、中央部上空では蒸発した溶媒が逃げにくく溶媒の蒸気圧が高く維持されやすいのに対し、端部上空では蒸発した溶媒が周囲に逃げやすく溶媒の蒸気圧が低くなりやすいからである。この蒸発速度の違いにより、溶液13の表層部では中央部から端部に向かう方向に溶液の流れ14が生じ、これに伴い、溶液13の深層部では端部から中央部に向かう方向に溶液の流れ15が生じる。溶液13の乾燥が進むと、溶液13の量が次第に減り(図1(b))、その分、機能性材料の濃度が高くなる。最終的には、溶液13中の溶媒が全て蒸発することで、機能性材料から構成される機能層16が形成される(図1(c))。 The applied solution 13 has a shape in which the central portion swells due to the surface tension of the solution 13. The solvent in the solution 13 gradually evaporates from the surface of the solution 13. At this time, as shown in FIG. 1A, the evaporation rate of the solvent at the end of the solution 13 is larger than the evaporation rate of the solvent at the center. This is because the evaporated solvent is difficult to escape over the central part and the vapor pressure of the solvent is easily maintained high, whereas the evaporated solvent easily escapes to the surroundings and tends to lower the solvent vapor pressure over the edge. Due to this difference in evaporation rate, a solution flow 14 is generated in the direction from the central portion to the end portion in the surface layer portion of the solution 13, and accordingly, in the deep layer portion of the solution 13, the solution flows in the direction from the end portion to the central portion. Stream 15 is generated. As the drying of the solution 13 proceeds, the amount of the solution 13 gradually decreases (FIG. 1B), and the concentration of the functional material increases accordingly. Eventually, all the solvent in the solution 13 evaporates to form the functional layer 16 made of a functional material (FIG. 1C).

 機能層16の形状は、溶液13の乾燥過程の序盤(図1(a))よりも終盤(図1(b))での溶液の形状や溶液中での機能性材料の振る舞いに大きく依存すると考えられる。発明者らは、機能層16の端部と中央部の膜厚差を低減するには、溶液13の乾燥過程の終盤での溶液13の形状や機能性材料の振る舞いを決定付けるパラメータを適切に調整すればよいと考えた。さらに、発明者らは、これらのパラメータとして、200℃以上の沸点を有する高沸点溶媒の粘度と表面張力に着目した。まず、高沸点溶媒に着目したのは、溶液の乾燥過程の終盤の溶液13の物性は高沸点溶媒の物性に大きく依存すると考えられるからである。例えば、溶液13が高沸点溶媒と低沸点溶媒を含む場合、溶液13の乾燥過程では低沸点溶媒が高沸点溶媒よりも先に蒸発し、溶液13の乾燥過程の終盤では高沸点溶媒が多く残存することになる。また、溶液13が高沸点溶媒を含み低沸点溶媒を含まない場合は、溶液13の乾燥過程の序盤でも終盤でも高沸点溶媒しか存在しない。従って、溶液13が高沸点溶媒を含む場合、溶液13の乾燥過程の終盤の溶液13の物性は高沸点溶媒の物性に大きく依存すると言える。また、高沸点溶媒の物性の中でも粘度と表面張力に着目したのは、粘度が溶液中での機能性材料の振る舞いに影響を与え、表面張力が溶液の形状に影響を与えると考えられるからである。 The shape of the functional layer 16 is more dependent on the shape of the solution at the end (FIG. 1 (b)) and the behavior of the functional material in the solution than at the beginning of the drying process of the solution 13 (FIG. 1 (a)). Conceivable. The inventors appropriately set parameters that determine the shape of the solution 13 and the behavior of the functional material at the end of the drying process of the solution 13 in order to reduce the film thickness difference between the end and the center of the functional layer 16. I thought it should be adjusted. Furthermore, the inventors paid attention to the viscosity and surface tension of a high-boiling solvent having a boiling point of 200 ° C. or higher as these parameters. First, the high boiling point solvent is focused on because the physical properties of the solution 13 at the end of the drying process of the solution are considered to largely depend on the physical properties of the high boiling point solvent. For example, when the solution 13 includes a high-boiling solvent and a low-boiling solvent, the low-boiling solvent evaporates before the high-boiling solvent in the drying process of the solution 13, and a large amount of the high-boiling solvent remains at the end of the drying process of the solution 13. Will do. In addition, when the solution 13 includes a high boiling point solvent and does not include a low boiling point solvent, only the high boiling point solvent exists at the beginning and the end of the drying process of the solution 13. Therefore, when the solution 13 contains a high boiling point solvent, it can be said that the physical properties of the solution 13 at the end of the drying process of the solution 13 largely depend on the physical properties of the high boiling point solvent. The reason for focusing on viscosity and surface tension among the physical properties of high-boiling solvents is that viscosity affects the behavior of functional materials in solution, and surface tension is thought to affect the shape of the solution. is there.

 発明者らは、1または複数の溶媒成分を選択し、選択した溶媒成分を1または複数の体積比で混合することで、複数の溶媒を得た。そして、各溶媒を用いて機能層16を形成し、各々の機能層16の形状を観察した。この結果、溶液に含まれる高沸点溶媒の粘度と表面張力が特定の範囲内であれば、機能層16の端部と中央部との膜厚差を低減できることが判明した。 The inventors selected one or a plurality of solvent components, and obtained a plurality of solvents by mixing the selected solvent components in one or a plurality of volume ratios. And the functional layer 16 was formed using each solvent, and the shape of each functional layer 16 was observed. As a result, it has been found that if the viscosity and surface tension of the high-boiling solvent contained in the solution are within a specific range, the film thickness difference between the end portion and the central portion of the functional layer 16 can be reduced.

 <2> 本発明の一態様の概要
 本発明の一態様に係る溶液は、有機発光素子に含まれる機能層を構成する機能性材料と、溶媒とを含む。溶媒は、200℃以上の沸点を有する1または複数の溶媒成分から構成される高沸点溶媒を含む。高沸点溶媒は、13mPa・s以上25mPa・s以下の粘度と、33mN/m以上37mN/m以下の表面張力とを有する。
<2> Outline of One Aspect of the Invention A solution according to one aspect of the present invention includes a functional material that constitutes a functional layer included in an organic light-emitting element, and a solvent. The solvent includes a high boiling point solvent composed of one or more solvent components having a boiling point of 200 ° C. or higher. The high boiling point solvent has a viscosity of 13 mPa · s to 25 mPa · s and a surface tension of 33 mN / m to 37 mN / m.

 溶液中の高沸点溶媒の粘度と表面張力を上記範囲内とすることで、機能層の端部と中央部の膜厚差を低減することができる。 When the viscosity and surface tension of the high boiling point solvent in the solution are within the above ranges, the difference in film thickness between the end and the center of the functional layer can be reduced.

 なお、高沸点溶媒が複数の溶媒成分から構成される場合、高沸点溶媒の粘度は、溶媒成分の体積比とその溶媒成分の室温での粘度の積を溶媒成分毎に算出し、算出された各溶媒成分の積を足し合わせることにより得られる。高沸点溶媒の表面張力も、同様に、溶媒成分の体積比とその溶媒成分の室温での表面張力の積を溶媒成分毎に算出し、算出された各溶媒成分の積を足し合わせることにより得られる。 When the high boiling point solvent is composed of a plurality of solvent components, the viscosity of the high boiling point solvent was calculated by calculating the product of the volume ratio of the solvent component and the viscosity of the solvent component at room temperature for each solvent component. It is obtained by adding the product of each solvent component. Similarly, the surface tension of the high boiling point solvent is obtained by calculating the product of the volume ratio of the solvent component and the surface tension of the solvent component at room temperature for each solvent component, and adding the calculated product of each solvent component. It is done.

 また、高沸点溶媒の粘度が、15mPa・sより大きいこととしてもよい。 The viscosity of the high boiling point solvent may be greater than 15 mPa · s.

 また、高沸点溶媒を構成する1または複数の溶媒成分の少なくとも1つは、20mPa・s以上の粘度を有する高粘度溶媒であり、高沸点溶媒に占める高粘度溶媒の割合が35vol%以上であることとしてもよい。これにより、機能層における平坦領域の割合を高めることができる。 Further, at least one of the one or more solvent components constituting the high boiling point solvent is a high viscosity solvent having a viscosity of 20 mPa · s or more, and the proportion of the high viscosity solvent in the high boiling point solvent is 35 vol% or more. It is good as well. Thereby, the ratio of the flat area | region in a functional layer can be raised.

 また、高沸点溶媒に占める高粘度溶媒の割合が50vol%以上であることとしてもよい。これにより、機能層における平坦領域の割合をより一層高めることができる。 Further, the ratio of the high viscosity solvent to the high boiling point solvent may be 50 vol% or more. Thereby, the ratio of the flat area | region in a functional layer can be raised further.

 また、溶媒は、さらに、200℃未満の沸点を有する1または複数の溶媒成分から構成される低沸点溶媒を含み、溶液の粘度が、5mPa・s以上15mPa・s以下であることとしてもよい。溶液を塗布する場合、塗りやすさの観点から溶液の粘度には適切な範囲が存在する。ところが、上述の通り、高沸点溶媒の粘度は機能層の形状の平坦性の観点で決められるので、溶液の粘度が塗布に適切な範囲から外れる場合がある。そのため、溶液に低沸点溶媒を含めることで、溶液の粘度を適切な範囲に調整してもよい。溶液の粘度を5mPa・s以上15mPa・s以下とすることで、例えば、インクジェット方式の塗布方法に好適に利用することができる。 Further, the solvent may further include a low boiling point solvent composed of one or a plurality of solvent components having a boiling point of less than 200 ° C., and the viscosity of the solution may be 5 mPa · s or more and 15 mPa · s or less. When applying a solution, the viscosity of the solution has an appropriate range from the viewpoint of ease of application. However, as described above, the viscosity of the high-boiling solvent is determined from the viewpoint of the flatness of the shape of the functional layer, and thus the viscosity of the solution may deviate from a range suitable for application. Therefore, the viscosity of the solution may be adjusted to an appropriate range by including a low boiling point solvent in the solution. By setting the viscosity of the solution to 5 mPa · s or more and 15 mPa · s or less, it can be suitably used for, for example, an inkjet coating method.

 また、低沸点溶媒を構成する1または複数の溶媒成分は、何れも160℃より高い沸点を有することとしてもよい。これにより、溶液の塗布前に低沸点溶媒の一部が蒸発し、溶液の濃度や溶媒組成比が変化してしまうという事態を防止することができる。 Further, one or more solvent components constituting the low boiling point solvent may have a boiling point higher than 160 ° C. As a result, it is possible to prevent a situation in which a part of the low boiling point solvent evaporates before application of the solution and the concentration of the solution and the solvent composition ratio change.

 また、溶媒は、さらに、200℃未満の沸点を有する1または複数の溶媒成分から構成される低沸点溶媒を含み、溶媒に占める高沸点溶媒の割合が80%以下であることとしてもよい。これにより、コーヒーステイン現象の発生を抑制して良好な膜形状を得ることができる。 In addition, the solvent may further include a low-boiling solvent composed of one or more solvent components having a boiling point of less than 200 ° C., and the proportion of the high-boiling solvent in the solvent may be 80% or less. Thereby, generation | occurrence | production of a coffee stain phenomenon can be suppressed and a favorable film | membrane shape can be obtained.

 さらに、溶媒に占める前記高沸点溶媒の割合が60%以下であることしてもよい。 Furthermore, the proportion of the high boiling point solvent in the solvent may be 60% or less.

 本発明の一態様の有機発光素子の製造方法は、第1電極を形成し、第1電極の上方に機能性材料と溶媒とを含む溶液を塗布し、塗布された溶液を乾燥させることにより機能性材料から構成される機能層を第1電極の上方に形成し、機能層の上方に第2電極を形成する。ここで、溶媒が、200℃以上の沸点を有する1または複数の溶媒成分から構成される高沸点溶媒を含む。高沸点溶媒は、13mPa・s以上25mPa・s以下の粘度と、33mN/m以上37mN/m以下の表面張力とを有する。 The method for manufacturing an organic light-emitting element of one embodiment of the present invention functions by forming a first electrode, applying a solution containing a functional material and a solvent above the first electrode, and drying the applied solution. A functional layer made of a functional material is formed above the first electrode, and a second electrode is formed above the functional layer. Here, the solvent includes a high boiling point solvent composed of one or a plurality of solvent components having a boiling point of 200 ° C. or higher. The high boiling point solvent has a viscosity of 13 mPa · s to 25 mPa · s and a surface tension of 33 mN / m to 37 mN / m.

 これにより、機能層の端部と中央部の膜厚差を低減でき、その結果、良好な有機発光素子の発光特性を得ることができる。 Thereby, the film thickness difference between the end portion and the central portion of the functional layer can be reduced, and as a result, good light emission characteristics of the organic light emitting device can be obtained.

 <3> 第1実施形態(溶液)
 <3.1> 機能性材料
 溶液は、機能性材料を含む。機能性材料は、有機発光素子に含まれる機能層を構成する材料である。前述の通り、機能層は、例えば、発光層、ホール注入層、ホール輸送層、ホール注入兼輸送層、電子注入層、電子輸送層、および電子注入兼輸送層である。
<3> First embodiment (solution)
<3.1> Functional material The solution contains a functional material. The functional material is a material constituting the functional layer included in the organic light emitting element. As described above, the functional layer is, for example, a light emitting layer, a hole injection layer, a hole transport layer, a hole injection / transport layer, an electron injection layer, an electron transport layer, and an electron injection / transport layer.

 ホール注入層、ホール輸送層、ホール注入兼輸送層の材料としては、例えば、特許文献2に記載のトリアゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体及びピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、オキサゾール誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、ポリフィリン化合物、芳香族第三級アミン化合物及びスチリルアミン化合物、ブタジエン化合物、ポリスチレン誘導体、ヒドラゾン誘導体、トリフェニルメタン誘導体、テトラフェニルベンジン誘導体を利用である。 Examples of the material for the hole injection layer, the hole transport layer, and the hole injection / transport layer include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives described in Patent Document 2, phenylenediamine Derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, polyphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds, butadiene compounds, polystyrene derivatives, hydrazone derivatives , Triphenylmethane derivatives, and tetraphenylbenzine derivatives.

 発光層の材料としては、例えば、特許文献2に記載のオキシノイド化合物、ペリレン化合物、クマリン化合物、アザクマリン化合物、オキサゾール化合物、オキサジアゾール化合物、ペリノン化合物、ピロロピロール化合物、ナフタレン化合物、アントラセン化合物、フルオレン化合物、フルオランテン化合物、テトラセン化合物、ピレン化合物、コロネン化合物、キノロン化合物及びアザキノロン化合物、ピラゾリン誘導体及びピラゾロン誘導体、ローダミン化合物、クリセン化合物、フェナントレン化合物、シクロペンタジエン化合物、スチルベン化合物、ジフェニルキノン化合物、スチリル化合物、ブタジエン化合物、ジシアノメチレンピラン化合物、ジシアノメチレンチオピラン化合物、フルオレセイン化合物、ピリリウム化合物、チアピリリウム化合物、セレナピリリウム化合物、テルロピリリウム化合物、芳香族アルダジエン化合物、オリゴフェニレン化合物、チオキサンテン化合物、アンスラセン化合物、シアニン化合物、アクリジン化合物、8-ヒドロキシキノリン化合物の金属錯体、2-ビピリジン化合物の金属錯体、シッフ塩とIII族金属との錯体、オキシン金属錯体、希土類錯体等の蛍光物質を利用できる。 Examples of the material for the light emitting layer include the oxinoid compound, perylene compound, coumarin compound, azacoumarin compound, oxazole compound, oxadiazole compound, perinone compound, pyrrolopyrrole compound, naphthalene compound, anthracene compound, and fluorene compound described in Patent Document 2. , Fluoranthene compound, tetracene compound, pyrene compound, coronene compound, quinolone compound and azaquinolone compound, pyrazoline derivative and pyrazolone derivative, rhodamine compound, chrysene compound, phenanthrene compound, cyclopentadiene compound, stilbene compound, diphenylquinone compound, styryl compound, butadiene compound , Dicyanomethylenepyran compounds, dicyanomethylenethiopyran compounds, fluorescein compounds, pyrylium compounds Thiapyrylium compounds, serenapyrylium compounds, telluropyrylium compounds, aromatic aldadiene compounds, oligophenylene compounds, thioxanthene compounds, anthracene compounds, cyanine compounds, acridine compounds, metal complexes of 8-hydroxyquinoline compounds, metal complexes of 2-bipyridine compounds, Fluorescent materials such as Schiff salt and Group III metal complexes, oxine metal complexes, and rare earth complexes can be used.

 電子注入層、電子輸送層、電子注入兼輸送層の材料としては、例えば、特許文献2に記載のニトロ置換フルオレノン誘導体、チオピランジオキサイド誘導体、ジフェキノン誘導体、ペリレンテトラカルボキシル誘導体、アントラキノジメタン誘導体、フレオレニリデンメタン誘導体、アントロン誘導体、オキサジアゾール誘導体、ペリノン誘導体、キノリン錯体誘導体を利用できる。 Examples of the material for the electron injection layer, the electron transport layer, and the electron injection / transport layer include, for example, a nitro-substituted fluorenone derivative, a thiopyrandioxide derivative, a difequinone derivative, a perylenetetracarboxyl derivative, and an anthraquinodimethane derivative described in Patent Document 2. , Fluorenylidenemethane derivatives, anthrone derivatives, oxadiazole derivatives, perinone derivatives, and quinoline complex derivatives can be used.

 <3.2> 溶媒
 溶液は、機能性材料に加えて溶媒を含む。溶媒は、高沸点溶媒を含み、必要に応じて低沸点溶媒も含む。本明細書では、便宜上、高沸点と低沸点の境界を200℃とする。高沸点溶媒は、200℃以上の沸点を有する1または複数の溶媒成分から構成される。また、低沸点溶媒は、200℃未満の沸点を有する1または複数の溶媒成分から構成される。
<3.2> Solvent The solution contains a solvent in addition to the functional material. The solvent includes a high boiling point solvent, and optionally includes a low boiling point solvent. In this specification, the boundary between the high boiling point and the low boiling point is set to 200 ° C. for convenience. The high boiling point solvent is composed of one or more solvent components having a boiling point of 200 ° C. or higher. The low boiling point solvent is composed of one or more solvent components having a boiling point of less than 200 ° C.

 さらに、必要に応じて、高沸点溶媒を構成する1または複数の溶媒成分の少なくとも1つを高粘度溶媒とする。本明細書では、便宜上、高粘度と低粘度の境界を20mPa・sとする。 Furthermore, if necessary, at least one of one or a plurality of solvent components constituting the high boiling point solvent is used as a high viscosity solvent. In this specification, for the sake of convenience, the boundary between high viscosity and low viscosity is 20 mPa · s.

 溶媒成分としては、例えば、メタノール(Methanol)、エタノール(Ethanol)、プロパノール(Propanol)、イソプロピルアルコール(Isopropyl Alcohol)、ブタノール(Butanol)、イソブチルアルコール(Isobutyl Alcohol)、2-ブチルアルコール(sec-Butyl Alcohol)、tert-ブチルアルコール(tert-Butyl Alcohol)、エチレングリコール(Ethylene Glycol)、1,2-ジメトキシエタン(1,2-Dimethoxyethane)、ジエチルエーテル(Diethyl Ether)、ジイソプロピルエーテル(Diisopropyl Ether)、酢酸(Acetic Acid)、酢酸エチル(Ethyl Acetate)、無水酢酸(Acetic Anhydride)、テトラヒドロフラン(Tetrahydrofuran)、1,4-ジオキサン(1,4-Dioxane)、アセトン(Acetone)、エチルメチルケトン(Ethyl Methyl Ketone)、四塩化炭素(Carbon Tetrachloride)、クロロホルム(Chloroform)、ジクロロメタン(Dichloromethane)、1,2-ジクロロエタン(1,2-Dichloroethane)、ベンゼン(Benzene)、トルエン(Toluene)、キシレン(Xylene)、シクロヘキサン(Cyclohexane)、ペンタン(Pentane)、ヘキサン(Hexane)、ヘプタン(Heptane)、アセトニトリル(Acetonitrile)、ニトロメタン(Nitromethane)、N,N-ジメチルホルムアミド(N,N-Dimethylformamide)、ヘキサメチルリン酸トリアミド(Hexamethylphosphoric Triamide)、トリエチルアミン(Triethylamine)、ピリジン(Pyridine)、ジメチルスルホキシド(Dimethyl Slufoxide)、二硫化炭素(Carbon Disulfide)、1,3-ジメチル-2-イミダゾリジノン(1,3-Dimethyl-2-Imidazolidinone)、ジプロピレングリコール(Dipropylene Glycol)、ジエチレングリコールモノブチルエーテル(Diethylene glycol monobutyl ether)、エチレングリコールモノエチルエーテルアセテート(Ethylene glycol monoethyl ether acetate)、プロピレングリコール(Propylene Glycol)、2,3-ブタンジオール(2,3-Butanediol)、シクロヘキサノール(Cyclohexanol)、シクロヘキシルベンゼン(Cyclohexylbenzene)、エチレングリコールモノフェニルエーテル(Ethylene Glycol Monophenyl Ether)、エチレングリコールモノブチルエーテル(Ethylene Glycol Monobutyl Ether)を利用できる。 Examples of the solvent component include methanol, ethanol, propanol, isopropyl alcohol, butanol, butanol, isobutyl alcohol, and sec-butyl alcohol. ), Tert-butyl alcohol (tert-Butyl Alcohol), ethylene glycol (Ethylene Glycol), 1,2-dimethoxyethane, diethyl ether (Diethyl Ether), diisopropyl ether (Diisopropyl Ether), acetic acid ( Acetic Acid, Ethyl 酢 酸 Acetate, Acetic anhydride (Acetic Anhydride), Tetrahydrofuran, 1,4-Dioxane, Acetone, Ethyl methyl ketone (Ethyl Methyl Ketone), Carbon tetrachloride, Chloroform Dichloromethane, 1,2-Dichloroethane, Benzene, Toluene, Xylene, Cyclohexane, Pentane, Hexane, Heptane (Hexane) Heptane), acetonitrile (Acetonitrile), nitromethane (Nitromethane), N, N-dimethylformamide (N, N-Dimethylformamide), hexamethylphosphoric triamide, triethylamine, pyridine (Pyridine), dimethyl sulfoxide ( Dimethyl Sulfoxide), Carbon disulfide, 1,3-Dimethyl-2-imidazolidinone, Dipropylene グ リ コ ー ル Glycol, Diethylene glycol monobutyl ether ether), ethylene glycol Monoethyl ether acetate (Ethylene glycol monoethyl ether acetate), propylene glycol (Propylene Glycol), 2,3-butanediol (2,3-Butanediol), cyclohexanol, Cyclohexylbenzene, ethylene glycol monophenyl Ether (Ethylene Glycol Monophenyl Ether) and ethylene glycol monobutyl ether (Ethylene Glycol Monobutyl Ether) can be used.

 <3.3> 実験および考察
 まず、機能層の端部と中央部の膜厚差を低減するための溶媒の物性を求める実験について説明する。
<3.3> Experiment and Discussion First, an experiment for obtaining the physical properties of a solvent for reducing the difference in film thickness between the end and the center of the functional layer will be described.

 発明者らは、溶媒成分として、図2に示す溶媒を用意した。図2に、各溶媒成分の沸点、蒸気圧、粘度、表面張力を示す。発明者らは、これらの溶媒成分の中から1または複数の溶媒成分を選択し、選択した溶媒成分を適宜の体積比で混合することで、溶媒A、B、C、D、E、F、G、Hを得た。 The inventors prepared the solvent shown in FIG. 2 as the solvent component. FIG. 2 shows the boiling point, vapor pressure, viscosity, and surface tension of each solvent component. The inventors select one or a plurality of solvent components from among these solvent components, and mix the selected solvent components at an appropriate volume ratio, so that the solvents A, B, C, D, E, F, G and H were obtained.

 発明者らは、得られた溶媒A、B、C、D、E、F、G、Hを用いて基板上に機能層を形成した。機能層を構成する機能性材料は、各溶媒で共通とした。実験に用いた基板の平面図を図3(a)に示し、そのA-A断面図を図3(b)に示す。隔壁12は、ガラス製の基板11の機能層を形成する領域を囲む。隔壁12で区画された領域の長手方向の幅は約254μm、短手方向の幅は約60μmである。本実験では、機能層16の目標の膜厚を30nmとする。 The inventors formed a functional layer on the substrate using the obtained solvents A, B, C, D, E, F, G, and H. The functional material constituting the functional layer is common to each solvent. FIG. 3A shows a plan view of the substrate used in the experiment, and FIG. 3B shows a cross-sectional view taken along the line AA. The partition wall 12 surrounds a region where the functional layer of the glass substrate 11 is formed. The width in the longitudinal direction of the region partitioned by the partition 12 is about 254 μm, and the width in the short direction is about 60 μm. In this experiment, the target film thickness of the functional layer 16 is set to 30 nm.

 発明者らは、さらに、形成された機能層の形状を「平坦」、「凸状」または「凹状」に分類した。図4を用いて機能層の形状の分類手法を説明する。図4(a)は平坦を示し、図4(b)は凸状を示し、図4(c)は凹状を示す。 The inventors further classified the shape of the formed functional layer into “flat”, “convex” or “concave”. A method for classifying the shape of the functional layer will be described with reference to FIG. 4A shows flatness, FIG. 4B shows a convex shape, and FIG. 4C shows a concave shape.

 図4(a)に示すように、隔壁12の内周面は斜面になっているため、機能層16の長手方向両側が隔壁12に乗り上げた形となる。ここでは、機能層16の上面の基板11からの高さが200nmになる位置を基準位置と定義する。図4(a)の断面では、基準位置が2箇所存在する。これらの基準位置に挟まれる領域を機能層16の発光領域と定義する。そして、機能層16の発光領域の中心の位置を、機能層16の中央部Cと定義する。また、それぞれの基準位置から機能層16の発光領域の幅の12.5%だけ中央部C寄りの位置を、それぞれ機能層16の端部L、端部Rと定義する。そして、機能層16の中央部Cの膜厚をdC、端部Lの膜厚をdL、端部Rの膜厚dRとし、機能層16の端部と中央部との膜厚差Δdを以下の数式を用いて算出し、膜厚差Δdを用いて機能層16の形状を分類する。 As shown in FIG. 4A, since the inner peripheral surface of the partition wall 12 is an inclined surface, both longitudinal sides of the functional layer 16 ride on the partition wall 12. Here, the position where the height of the upper surface of the functional layer 16 from the substrate 11 is 200 nm is defined as the reference position. In the cross section of FIG. 4A, there are two reference positions. The region sandwiched between these reference positions is defined as the light emitting region of the functional layer 16. The position of the center of the light emitting region of the functional layer 16 is defined as the central portion C of the functional layer 16. Further, the positions near the central portion C by 12.5% of the width of the light emitting region of the functional layer 16 from the respective reference positions are defined as the end portion L and the end portion R of the functional layer 16, respectively. Then, the thickness of the central portion C of the functional layer 16 is d C , the thickness of the end portion L is d L , and the thickness of the end portion R is d R. Δd is calculated using the following formula, and the shape of the functional layer 16 is classified using the film thickness difference Δd.

 Δd=(dL+dR)/2-dC
 「平坦」は、膜厚差Δdの絶対値が中央部Cの膜厚dCの20%以下の場合とする。
Δd = (d L + d R ) / 2−d C
“Flat” means that the absolute value of the film thickness difference Δd is 20% or less of the film thickness d C of the central portion C.

 「凸状」は、膜厚差Δdの絶対値が中央部Cの膜厚dCの20%より大きく、且つ、膜厚差Δdが負の場合とする。 The “convex shape” is a case where the absolute value of the film thickness difference Δd is larger than 20% of the film thickness d C of the central portion C and the film thickness difference Δd is negative.

 「凹状」は、膜厚差Δdの絶対値が中央部Cの膜厚dCの20%より大きく、且つ、膜厚差Δdが正の場合とする。 The “concave shape” is a case where the absolute value of the film thickness difference Δd is larger than 20% of the film thickness d C of the central portion C and the film thickness difference Δd is positive.

 図5に、各溶媒を用いて形成した機能層の写真の一例と、機能層の形状の評価結果とを示す。これにより、機能性材料が共通していても溶媒が異なれば、機能層の形状が異なることが分かる。 FIG. 5 shows an example of a photograph of a functional layer formed using each solvent and an evaluation result of the shape of the functional layer. Thereby, even if a functional material is common, if a solvent differs, it turns out that the shape of a functional layer differs.

 図6に、機能層の形状の評価結果、溶液中の高沸点溶媒の粘度、溶液中の高沸点溶媒の表面張力を示し、図7に、各溶媒の高沸点溶媒の粘度と高沸点溶媒の表面張力をプロットしたグラフを示す。 FIG. 6 shows the evaluation results of the shape of the functional layer, the viscosity of the high boiling point solvent in the solution, and the surface tension of the high boiling point solvent in the solution. FIG. 7 shows the viscosity of the high boiling point solvent and the high boiling point solvent in each solvent. The graph which plotted surface tension is shown.

 図7において、溶媒A、Bを含むグループと溶媒C、Eを含むグループに着目すると、高沸点溶媒の粘度が概ね同じ場合、高沸点溶媒の表面張力が大きくなれば凸状となり、高沸点溶媒の表面張力が小さくなれば凹状となる傾向が読み取れる。また、図7において、溶媒C、Eを含むグループと溶媒D、F、Gを含むグループに着目すると、高沸点溶媒の表面張力が概ね同じ場合、高沸点溶媒の粘度が大きくなるほど平坦化する傾向が読み取れる。このことから、機能層の形状を平坦にするには、溶液中の高沸点溶媒の粘度と表面張力を適切な範囲に調整することが重要であると言える。 In FIG. 7, when focusing on the group containing the solvents A and B and the group containing the solvents C and E, when the viscosity of the high-boiling solvent is substantially the same, the surface becomes convex as the surface tension of the high-boiling solvent increases. It can be seen that the surface tension of the film becomes concave as the surface tension decreases. Further, in FIG. 7, when attention is paid to the group including the solvents C and E and the group including the solvents D, F, and G, when the surface tension of the high boiling point solvent is substantially the same, the tendency of flattening as the viscosity of the high boiling point solvent increases. Can be read. From this, it can be said that in order to make the shape of the functional layer flat, it is important to adjust the viscosity and the surface tension of the high boiling point solvent in the solution to an appropriate range.

 本実験では、溶媒D、F、Gを含むグループを用いると、機能層の形状が平坦になることが判明した。このことから、機能層の形状を平坦にするには、溶液中の高沸点溶媒の粘度を13mPa・s以上25mPa・s以下とし、溶液中の高沸点溶媒の表面張力を33mN/m以上37mN/m以下とすればよいことが分かる。また、高沸点溶媒の粘度が大きくなるほど平坦化する傾向があるので、溶液中の高沸点溶媒の粘度を15mPa・sより大きくするとより好ましい。また、溶液中の高沸点溶媒の表面張力の範囲の下限を33mN/mに代えて34mN/mにしてもよい。溶液中の高沸点溶媒の表面張力の範囲の上限を、37mN/mに代えて36mN/mにしてもよい。なお、溶液中の高沸点溶媒の粘度を25mPa・s以下とすることで、インクジェット方式の塗布方法に好適に利用することができる。 In this experiment, it was found that when a group containing solvents D, F, and G was used, the shape of the functional layer became flat. From this, in order to flatten the shape of the functional layer, the viscosity of the high boiling point solvent in the solution is 13 mPa · s to 25 mPa · s, and the surface tension of the high boiling point solvent in the solution is 33 mN / m to 37 mN / s. It can be seen that it should be less than m. Further, since the higher the boiling point of the solvent, the higher the tendency of the flattening, the more preferable the viscosity of the high boiling point solvent in the solution is greater than 15 mPa · s. Further, the lower limit of the surface tension range of the high boiling point solvent in the solution may be 34 mN / m instead of 33 mN / m. The upper limit of the surface tension range of the high-boiling solvent in the solution may be 36 mN / m instead of 37 mN / m. In addition, by setting the viscosity of the high boiling point solvent in the solution to 25 mPa · s or less, it can be suitably used for an ink jet method.

 発明者らは、さらに、撥液性を有する平坦な基板上に機能層を形成し、形成された機能層の形状を観察した。実験は、溶液を10滴基板上に滴下し、滴下した溶液を真空乾燥させ、形成された機能層の形状をレーザー顕微鏡(VK-9700、キーエンス社)により測定した。図8に溶媒毎の機能層の平面形状と断面形状とを示す。平面形状の画像のスケールは各溶媒で共通である。また、断面形状の画像のスケールは各溶媒で共通である。これによると、溶媒D、F、Gを含むグループ(図7で機能層の形状が平坦)と溶媒A、B、C、Eを含むグループ(図7で機能層の形状が凸状または凹状)とで、機能層の形状が異なることが分かる。溶媒D、F、Gを含むグループでは、いわゆるコーヒーステイン現象が生じており、溶媒A、B、C、Eを含むグループでは、コーヒーステイン現象が生じていない。これらの差異の原因は、溶媒中に占める高沸点溶媒の割合によるものと考えられる。高沸点溶媒の割合は、溶媒Aで33%、溶媒Bで33%、溶媒Cで60%、溶媒Dで100%、溶媒Eで53%、溶媒Fで83%、溶媒Gで83%である。高沸点溶媒の割合が大きいと、溶液の乾燥過程において対流が発生しやすく、その結果、コーヒーステイン現象が生じると考えられる。一般には、コーヒーステイン現象が生じないほうが良好な膜形状が得られると考えられている。従って、高沸点溶媒の粘度および表面張力については、溶媒D、F、Gを含むグループと同程度(13mPa・s以上25mPa・s以下、33mN/m以上37mN/m以下)としつつ、さらに、高沸点溶媒の割合を溶媒D、F、Gを含むグループよりも下げることが好ましい(80%以下)。さらには、溶媒A、B、C、Eと同程度まで下げてもよい(60%以下)。これにより、より良好な膜形状を得ることができる。なお、高沸点溶媒の割合は、低沸点溶媒の添加により容易に下げることができる。 The inventors further formed a functional layer on a flat substrate having liquid repellency, and observed the shape of the formed functional layer. In the experiment, 10 drops of the solution were dropped on a substrate, the dropped solution was vacuum-dried, and the shape of the formed functional layer was measured by a laser microscope (VK-9700, Keyence). FIG. 8 shows the planar shape and cross-sectional shape of the functional layer for each solvent. The scale of the planar image is common to each solvent. The scale of the cross-sectional image is common to each solvent. According to this, the group including the solvents D, F, and G (the shape of the functional layer is flat in FIG. 7) and the group including the solvents A, B, C, and E (the shape of the functional layer is convex or concave in FIG. 7). It can be seen that the shape of the functional layer is different. In the group including the solvents D, F, and G, a so-called coffee stain phenomenon occurs, and in the group including the solvents A, B, C, and E, the coffee stain phenomenon does not occur. The cause of these differences is considered to be due to the proportion of the high boiling point solvent in the solvent. The proportion of the high boiling point solvent is 33% for solvent A, 33% for solvent B, 60% for solvent C, 100% for solvent D, 53% for solvent E, 83% for solvent F, and 83% for solvent G. . If the ratio of the high boiling point solvent is large, convection is likely to occur during the drying process of the solution, and as a result, the coffee stain phenomenon is considered to occur. In general, it is considered that a better film shape can be obtained when the coffee stain phenomenon does not occur. Accordingly, the viscosity and surface tension of the high-boiling solvent are about the same as those of the group containing the solvents D, F, and G (13 mPa · s to 25 mPa · s, 33 mN / m to 37 mN / m), and higher. It is preferable to lower the boiling point solvent ratio than the group containing the solvents D, F and G (80% or less). Furthermore, it may be lowered to the same level as the solvents A, B, C and E (60% or less). Thereby, a better film shape can be obtained. In addition, the ratio of the high boiling point solvent can be easily lowered by the addition of the low boiling point solvent.

 次に、機能層の発光領域に占める平坦領域の割合を大きくするための溶媒の物性を求める実験について説明する。 Next, an experiment for determining the physical properties of the solvent for increasing the ratio of the flat region to the light emitting region of the functional layer will be described.

 発明者らは、複数の溶媒を用意し、各溶媒を用いて機能層を形成し、形成された機能層の発光領域に占める平坦領域の割合を調べた。ここで、平坦領域は、図3(a)の断面において、機能層の膜厚が目標の膜厚(この例では30nm)から±20%の範囲内に収まる領域の長さとする。 The inventors prepared a plurality of solvents, formed a functional layer using each solvent, and examined a ratio of a flat region in a light emitting region of the formed functional layer. Here, in the cross section of FIG. 3A, the flat region is the length of a region where the functional layer thickness falls within a range of ± 20% from the target film thickness (30 nm in this example).

 図9に、各溶媒の高沸点溶媒に占める高粘度溶媒と、発光領域に占める平坦領域の平坦領域の割合をプロットしたグラフを示す。高粘度溶媒の割合が0vol%の溶媒のグループでは、発光領域に占める平坦領域の割合が40%~60%の範囲に分布している。高粘度溶媒の割合が35vol%付近の溶媒のグループでは、発光領域に占める平坦領域の割合が60%~70%の範囲に分布している。高粘度溶媒の割合が50vol%の溶媒のグループでは、発光領域に占める平坦領域の割合が75%~85%の範囲に分布している。このように、高粘度溶媒の割合が35vol%付近の溶媒のグループは、高粘度溶媒の割合が0vol%の溶媒のグループよりも発光領域に占める平坦領域の割合が大きい。また、高粘度溶媒の割合が50vol%の溶媒のグループは、発光領域に占める平坦領域の割合がさらに大きく、概ね75%~85% 程度となる。従って、高沸点溶媒に占める高粘度溶媒の割合を35vol%以上とすることで機能層の平坦性を高めることができる。また、高粘度溶媒の割合を50vol%以上とするのがより好ましい。 FIG. 9 is a graph plotting the ratio of the high-viscosity solvent occupying the high boiling point solvent of each solvent and the flat area of the flat area occupying the light-emitting area. In the solvent group in which the proportion of the high-viscosity solvent is 0 vol%, the proportion of the flat region in the light emitting region is distributed in the range of 40% to 60%. In the solvent group in which the proportion of the high-viscosity solvent is around 35 vol%, the proportion of the flat region in the light emitting region is distributed in the range of 60% to 70%. In the solvent group in which the proportion of the high-viscosity solvent is 50 vol%, the proportion of the flat region in the light emitting region is distributed in the range of 75% to 85%. As described above, the solvent group in which the proportion of the high-viscosity solvent is around 35 vol% has a larger proportion of the flat region in the light emitting region than the solvent group in which the proportion of the high-viscosity solvent is 0 vol%. Further, in the solvent group in which the proportion of the high-viscosity solvent is 50 vol%, the proportion of the flat region in the light emitting region is further large, which is about 75% to 85%. Therefore, the flatness of the functional layer can be improved by setting the proportion of the high viscosity solvent in the high boiling point solvent to 35 vol% or more. Further, the ratio of the high viscosity solvent is more preferably 50 vol% or more.

 次に、機能性材料の分子量について検討する。図10に、溶液の粘度における溶液中の機能性材料の濃度の依存性を示す。溶媒を共通として機能性材料を異ならせた4種類の溶液を用意し、各溶液について溶液中の機能性材料の濃度を異ならせた場合の溶液の粘度の変化を測定した。これによると、機能性材料の濃度が大きいほど溶液の粘度が大きくなることが分かる。さらに詳細に見ると、機能性材料が低分子材料の場合は高分子材料の場合に比べて機能性材料の濃度の変化に対する溶液の粘度の変化の割合が小さいことが分かる。 Next, consider the molecular weight of functional materials. FIG. 10 shows the dependence of the concentration of the functional material in the solution on the viscosity of the solution. Four types of solutions with different functional materials were prepared using a common solvent, and the change in the viscosity of the solution when the concentration of the functional material in the solution was varied for each solution was measured. According to this, it turns out that the viscosity of a solution becomes large, so that the density | concentration of a functional material is large. In more detail, it can be seen that when the functional material is a low molecular material, the ratio of the change in the viscosity of the solution to the change in the concentration of the functional material is smaller than in the case of the high molecular material.

 溶液を基板上に塗布し、塗布された溶液を乾燥させて機能層を形成する工程では、溶液の乾燥の過程で溶媒の蒸発に伴い機能性材料の濃度が大きくなる。図10は、溶液の乾燥の過程で機能性材料の濃度の上昇によっても、溶液の粘度が大きくなることを示している。溶液の粘度が大きくなると、溶液の流れが弱くなり、機能性材料の振る舞いに与える影響が小さくなる。ところで、図10によると、機能性材料が低分子材料の場合は高分子材料の場合に比べて機能性材料の濃度の変化に対する溶液の粘度の変化の割合が小さい。そのため、機能性材料が高分子材料の場合は、溶液の流れが弱くなりやすく、機能性材料の振る舞いに与える影響が小さい。これに対し、機能性材料が低分子材料の場合は、溶液の流れが弱くなりにくく、機能性材料の振る舞いに与える影響が大きい。即ち、機能層の形状を平坦にするのは、機能性材料が高分子材料の場合も低分子材料の場合も困難性があるが、低分子材料の場合に特に困難性が高いと言える。従って、高沸点溶媒の粘度と表面張力を適切な範囲に設定した溶媒は、機能性材料が高分子材料の場合も低分子材料の場合も適用可能であるが、低分子材料の場合に特に有用である。なお、本明細書では、低分子材料とは、Mark-Houwink-Sakurada式が成り立たないものを言う。分子量としては、数千以下である。 In the step of applying the solution onto the substrate and drying the applied solution to form the functional layer, the concentration of the functional material increases as the solvent evaporates during the drying of the solution. FIG. 10 shows that the viscosity of the solution increases as the concentration of the functional material increases in the course of drying the solution. When the viscosity of the solution is increased, the flow of the solution is weakened, and the influence on the behavior of the functional material is reduced. By the way, according to FIG. 10, when the functional material is a low molecular material, the ratio of the change in the viscosity of the solution with respect to the change in the concentration of the functional material is smaller than in the case of the high molecular material. For this reason, when the functional material is a polymer material, the flow of the solution tends to be weak, and the influence on the behavior of the functional material is small. On the other hand, when the functional material is a low molecular material, the flow of the solution is difficult to weaken, and the influence on the behavior of the functional material is great. In other words, it can be said that flattening the shape of the functional layer is difficult when the functional material is a high molecular material or a low molecular material, but is particularly difficult when the functional material is a low molecular material. Therefore, a solvent in which the viscosity and surface tension of the high-boiling solvent are set to appropriate ranges can be applied to the case where the functional material is a high molecular material or a low molecular material, but is particularly useful in the case of a low molecular material. It is. Note that in this specification, the low molecular weight material refers to a material for which the Mark-Houwink-Sakurada equation does not hold. The molecular weight is several thousand or less.

 <4> 第2実施形態(有機発光素子の製造方法)
 図11に有機発光素子の製造方法を説明するための断面図を示す。
<4> Second Embodiment (Method for Manufacturing Organic Light-Emitting Element)
FIG. 11 is a cross-sectional view for explaining a method for manufacturing an organic light emitting device.

 まず、基板101を用意し、基板101上に第1電極102を形成する(図11(a))。 First, the substrate 101 is prepared, and the first electrode 102 is formed on the substrate 101 (FIG. 11A).

 次に、基板101上に隔壁層103を形成する(図11(b))。隔壁層103は、電気絶縁性であり、第1電極102の上方に開口を有する。隔壁層103の開口の周囲の部分が隔壁として機能する。図12に、隔壁層103の形状を示す。 Next, the partition layer 103 is formed on the substrate 101 (FIG. 11B). The partition layer 103 is electrically insulating and has an opening above the first electrode 102. A portion around the opening of the partition layer 103 functions as a partition. FIG. 12 shows the shape of the partition wall layer 103.

 次に、第1電極の上方の隔壁層103により区画された領域に溶液104を塗布する。溶液104は、機能性材料と溶媒とを含む。本例では、機能性材料は、ホール注入兼輸送層を形成するための材料として説明する。溶媒は、200℃以上の沸点を有する1または複数の溶媒成分から構成される高沸点溶媒を含む。高沸点溶媒は、13mPa・s以上25mPa・s以下の粘度と、33mN/m以上37mN/m以下の表面張力とを有する。 Next, the solution 104 is applied to the region partitioned by the partition layer 103 above the first electrode. The solution 104 includes a functional material and a solvent. In this example, the functional material will be described as a material for forming the hole injection / transport layer. The solvent includes a high boiling point solvent composed of one or more solvent components having a boiling point of 200 ° C. or higher. The high boiling point solvent has a viscosity of 13 mPa · s to 25 mPa · s and a surface tension of 33 mN / m to 37 mN / m.

 次に、塗布された溶液104を乾燥させることにより、第1電極102の上方にホール注入兼輸送層105を形成する(図11(d))。乾燥は、大気圧中または真空中において、加熱または非加熱で行なわれる。 Next, the applied solution 104 is dried to form a hole injection / transport layer 105 above the first electrode 102 (FIG. 11D). Drying is performed at atmospheric pressure or in vacuum, with or without heating.

 次に、ホール注入兼輸送層105の上方に発光層106を形成し(図11(e))、発光層106の上方に電子注入兼輸送層107を形成し(図11(f))、電子注入兼輸送層107の上方に第2電極108を形成する(図11(g))。 Next, the light emitting layer 106 is formed above the hole injection / transport layer 105 (FIG. 11E), and the electron injection / transport layer 107 is formed above the light emitting layer 106 (FIG. 11F). A second electrode 108 is formed above the injection / transport layer 107 (FIG. 11G).

 これにより、ホール注入兼輸送層105の端部と中央部の膜厚差を低減でき、その結果、良好な有機発光素子の発光特性を得ることができる。 Thereby, the difference in film thickness between the end portion and the central portion of the hole injection / transport layer 105 can be reduced, and as a result, good light emission characteristics of the organic light emitting device can be obtained.

 なお、溶媒は、上記の特徴だけでなく、第1実施形態に開示された他の特徴を有していてもよい。例えば、高沸点溶媒の粘度が、15mPa・sより大きくてもよい。また、高沸点溶媒に占める高粘度溶媒の割合が35vol%以上、あるいは、50vol%以上としてもよい。 In addition, the solvent may have other features disclosed in the first embodiment in addition to the above features. For example, the viscosity of the high boiling point solvent may be greater than 15 mPa · s. Further, the ratio of the high viscosity solvent to the high boiling point solvent may be 35 vol% or more, or 50 vol% or more.

 なお、溶媒は、200℃未満の沸点を有する1または複数の溶媒成分から構成される低沸点溶媒を含み、溶液の粘度が、5mPa・s以上15mPa・s以下であることとしてもよい。溶液の粘度をこの範囲にすることで、インクジェット方式の塗布方法に好適に利用することができる。また、低沸点溶媒を構成する1または複数の溶媒成分は、何れも160℃より高い沸点を有することとしてもよい。これにより、溶液の塗布前に低沸点溶媒の一部が蒸発し、溶液の濃度や溶媒組成比が変化してしまうという事態を防止することができる。 The solvent may include a low boiling point solvent composed of one or a plurality of solvent components having a boiling point of less than 200 ° C., and the viscosity of the solution may be 5 mPa · s or more and 15 mPa · s or less. By setting the viscosity of the solution within this range, it can be suitably used for an ink jet method. One or more solvent components constituting the low boiling point solvent may all have a boiling point higher than 160 ° C. As a result, it is possible to prevent a situation in which a part of the low boiling point solvent evaporates before application of the solution and the concentration of the solution and the solvent composition ratio change.

 なお、上記の例では、溶液の塗布により形成される機能層として、ホール注入兼輸送層105を例示しているが、これに限られない。ホール注入兼輸送層105に代えて、発光層106または電子注入兼輸送層107が溶液の塗布により形成されてもよい。あるいは、これらのうちの複数の機能層が溶液の塗布により形成されていてもよい。 In the above example, the hole injection / transport layer 105 is illustrated as a functional layer formed by application of a solution, but is not limited thereto. Instead of the hole injection / transport layer 105, the light emitting layer 106 or the electron injection / transport layer 107 may be formed by application of a solution. Or several of these functional layers may be formed by application | coating of the solution.

 また、上記の例では、第1電極、ホール注入兼輸送層、発光層、電子注入兼輸送層、第2電極の積層構造であるが、これに限られない。 In the above example, the first electrode, the hole injection / transport layer, the light emitting layer, the electron injection / transport layer, and the second electrode are stacked, but the present invention is not limited to this.

 また、上記の例では、隔壁層103が図12に示す形状であるが、これに限れない。例えば、図13に示す形状の隔壁層203を利用してもよい。隔壁層203は、複数の第1バンク203aと複数の第2バンク203bとを含む。第1バンク203aは、発光領域の長手方向に沿う。第2バンク203bは、隣り合う第1バンク203a間に存在し、発光領域の短手方向に沿う。第2バンク203bの高さは第1バンク203aの高さよりも低い。 In the above example, the partition wall layer 103 has the shape shown in FIG. 12, but the present invention is not limited to this. For example, a partition wall layer 203 having a shape shown in FIG. 13 may be used. The partition layer 203 includes a plurality of first banks 203a and a plurality of second banks 203b. The first bank 203a is along the longitudinal direction of the light emitting region. The second bank 203b exists between the adjacent first banks 203a and extends along the short direction of the light emitting region. The height of the second bank 203b is lower than the height of the first bank 203a.

 図14に、図13の隔壁層を利用した場合の溶液の乾燥過程を示す。 FIG. 14 shows a drying process of the solution when the partition wall layer of FIG. 13 is used.

 隔壁層203を利用した場合、隔壁層203により区画された領域(以下、「区画領域」という)に塗布された溶液204は、第2バンク203bを超えて隣りの区画領域まで達している(図14(a))。溶液204の乾燥の過程で、溶液204が区画領域に収まり(図14(b))、さらなる乾燥を経て、第1電極102の上方の区画領域に機能層205が形成される。隔壁層203を利用した場合でも、溶液204の乾燥過程の終盤(図14(b))は、隔壁層103を利用した場合と同様の状況となる。従って、隔壁層203を利用した場合でも、隔壁層103を利用した場合と同様の効果を得ることができる。 When the partition layer 203 is used, the solution 204 applied to a region partitioned by the partition layer 203 (hereinafter referred to as “partition region”) reaches the adjacent partition region beyond the second bank 203b (FIG. 14 (a)). In the process of drying the solution 204, the solution 204 is accommodated in the partition region (FIG. 14B), and after further drying, the functional layer 205 is formed in the partition region above the first electrode 102. Even when the partition wall layer 203 is used, the final stage of the drying process of the solution 204 (FIG. 14B) is the same situation as when the partition wall layer 103 is used. Therefore, even when the partition wall layer 203 is used, the same effect as when the partition wall layer 103 is used can be obtained.

 <5> 第3実施形態(有機表示装置)
 上記の有機発光素子は、有機表示装置に利用可能である。図15に、有機表示装置の機能ブロックを示す。図16に、有機表示装置の外観を例示する。有機表示装置20は、有機表示パネル21と、これに電気的に接続された駆動制御部22とを備える。有機表示パネル21は、図11(g)に示す有機発光素子を有する。駆動制御部22は、第1電極102と第2電極108の間に電圧を印加する駆動回路23と、駆動回路23の動作を制御する制御回路24とを含む。
<5> Third embodiment (organic display device)
Said organic light emitting element is applicable to an organic display apparatus. FIG. 15 shows functional blocks of the organic display device. FIG. 16 illustrates the appearance of the organic display device. The organic display device 20 includes an organic display panel 21 and a drive control unit 22 electrically connected thereto. The organic display panel 21 has the organic light emitting element shown in FIG. The drive control unit 22 includes a drive circuit 23 that applies a voltage between the first electrode 102 and the second electrode 108, and a control circuit 24 that controls the operation of the drive circuit 23.

 本発明の一態様は、例えば、有機発光素子に利用可能である。 One embodiment of the present invention can be used for, for example, an organic light-emitting element.

   11  基板
   12  隔壁
   13  溶液
   16  機能層
   20  有機表示装置
   21  有機表示パネル
   22  駆動制御部
   23  駆動回路
   24  制御回路
  101  基板
  102  第1電極
  103  隔壁
  103  隔壁層
  104  溶液
  105  ホール注入兼輸送層
  106  発光層
  107  電子注入兼輸送層
  108  第2電極
  203  隔壁層
  203a バンク
  203b バンク
  204  溶液
  205  機能層
DESCRIPTION OF SYMBOLS 11 Substrate 12 Partition 13 Solution 16 Functional layer 20 Organic display device 21 Organic display panel 22 Drive controller 23 Drive circuit 24 Control circuit 101 Substrate 102 First electrode 103 Partition 103 Partition wall 104 Solution 105 Hole injection / transport layer 106 Light emitting layer 107 Electron injection / transport layer 108 Second electrode 203 Partition layer 203a Bank 203b Bank 204 Solution 205 Functional layer

Claims (16)

 有機発光素子に含まれる機能層を形成するための溶液であって、前記機能層を構成する機能性材料と、溶媒とを含み、前記溶媒が、200℃以上の沸点を有する1または複数の溶媒成分から構成される高沸点溶媒を含み、前記高沸点溶媒が、13mPa・s以上25mPa・s以下の粘度と、33mN/m以上37mN/m以下の表面張力とを有する溶液。 A solution for forming a functional layer included in an organic light-emitting device, comprising a functional material constituting the functional layer and a solvent, wherein the solvent has a boiling point of 200 ° C. or higher. A solution comprising a high-boiling solvent composed of components, wherein the high-boiling solvent has a viscosity of from 13 mPa · s to 25 mPa · s and a surface tension of from 33 mN / m to 37 mN / m.  前記高沸点溶媒の粘度が、15mPa・sより大きい、請求項1に記載の溶液。 The solution according to claim 1, wherein the viscosity of the high boiling point solvent is greater than 15 mPa · s.  前記高沸点溶媒を構成する前記1または複数の溶媒成分の少なくとも1つは、20mPa・s以上の粘度を有する高粘度溶媒であり、前記高沸点溶媒に占める前記高粘度溶媒の割合が35vol%以上である、請求項1に記載の溶液。 At least one of the one or more solvent components constituting the high-boiling solvent is a high-viscosity solvent having a viscosity of 20 mPa · s or more, and the proportion of the high-viscosity solvent in the high-boiling solvent is 35 vol% or more. The solution according to claim 1, wherein  前記高沸点溶媒に占める前記高粘度溶媒の割合が50vol%以上である、請求項3に記載の溶液。 The solution according to claim 3, wherein the ratio of the high-viscosity solvent to the high-boiling solvent is 50 vol% or more.  前記溶媒は、さらに、200℃未満の沸点を有する1または複数の溶媒成分から構成される低沸点溶媒を含み、前記溶液の粘度が、5mPa・s以上15mPa・s以下である、請求項1に記載の溶液。 2. The solvent according to claim 1, further comprising a low-boiling solvent composed of one or more solvent components having a boiling point of less than 200 ° C., wherein the viscosity of the solution is 5 mPa · s or more and 15 mPa · s or less. The solution described.  前記低沸点溶媒を構成する前記1または複数の溶媒成分は、何れも160℃より高い沸点を有する、請求項5に記載の溶液。 The solution according to claim 5, wherein each of the one or more solvent components constituting the low-boiling solvent has a boiling point higher than 160 ° C.  前記溶媒は、さらに、200℃未満の沸点を有する1または複数の溶媒成分から構成される低沸点溶媒を含み、前記溶媒に占める前記高沸点溶媒の割合が80%以下である、請求項1に記載の溶液。 2. The solvent according to claim 1, further comprising a low-boiling solvent composed of one or a plurality of solvent components having a boiling point of less than 200 ° C., wherein the proportion of the high-boiling solvent in the solvent is 80% or less. The solution described.  前記溶媒に占める前記高沸点溶媒の割合が60%以下である、請求項7に記載の溶液。 The solution according to claim 7, wherein the proportion of the high boiling point solvent in the solvent is 60% or less.  第1電極を形成し、
 前記第1電極の上方に、機能性材料と溶媒とを含む溶液を塗布し、
 前記塗布された溶液を乾燥させることにより前記機能性材料から構成される機能層を前記第1電極の上方に形成し、
 前記機能層の上方に第2電極を形成し、
 前記溶媒が、200℃以上の沸点を有する1または複数の溶媒成分から構成される高沸点溶媒を含み、前記高沸点溶媒が、13mPa・s以上25mPa・s以下の粘度と、33mN/m以上37mN/m以下の表面張力とを有する、
 有機発光素子の製造方法。
Forming a first electrode;
A solution containing a functional material and a solvent is applied above the first electrode,
Forming a functional layer composed of the functional material above the first electrode by drying the applied solution;
Forming a second electrode above the functional layer;
The solvent includes a high boiling point solvent composed of one or a plurality of solvent components having a boiling point of 200 ° C. or higher, and the high boiling point solvent has a viscosity of 13 mPa · s to 25 mPa · s, and 33 mN / m to 37 mN. having a surface tension of / m or less,
Manufacturing method of organic light emitting element.
 前記高沸点溶媒の粘度が、15mPa・sより大きい、請求項9に記載の有機発光素子の製造方法。 The method for producing an organic light-emitting device according to claim 9, wherein the viscosity of the high boiling point solvent is greater than 15 mPa · s.  前記高沸点溶媒を構成する前記1または複数の溶媒成分の少なくとも1つは、20mPa・s以上の粘度を有する高粘度溶媒であり、前記高沸点溶媒に占める前記高粘度溶媒の割合が35vol%以上である、請求項9に記載の有機発光素子の製造方法。 At least one of the one or more solvent components constituting the high-boiling solvent is a high-viscosity solvent having a viscosity of 20 mPa · s or more, and the proportion of the high-viscosity solvent in the high-boiling solvent is 35 vol% or more. The manufacturing method of the organic light emitting element of Claim 9 which is.  前記高沸点溶媒に占める前記高粘度溶媒の割合が50vol%以上である、請求項11に記載の有機発光素子の製造方法。 The method for producing an organic light-emitting element according to claim 11, wherein the proportion of the high-viscosity solvent in the high-boiling solvent is 50 vol% or more.  前記溶媒は、さらに、200℃未満の沸点を有する1または複数の溶媒成分から構成される低沸点溶媒を含み、前記溶液の粘度が、5mPa・s以上15mPa・s以下である、請求項9に記載の有機発光素子の製造方法。 10. The solvent according to claim 9, wherein the solvent further includes a low boiling point solvent composed of one or more solvent components having a boiling point of less than 200 ° C., and the viscosity of the solution is 5 mPa · s or more and 15 mPa · s or less. The manufacturing method of the organic light emitting element of description.  前記低沸点溶媒を構成する前記1または複数の溶媒成分は、何れも160℃より高い沸点を有する、請求項13に記載の有機発光素子の製造方法。 The method for producing an organic light-emitting element according to claim 13, wherein each of the one or more solvent components constituting the low-boiling solvent has a boiling point higher than 160 ° C.  前記溶媒は、さらに、200℃未満の沸点を有する1または複数の溶媒成分から構成される低沸点溶媒を含み、前記溶媒に占める前記高沸点溶媒の割合が80%以下である、請求項9に記載の有機発光素子の製造方法。 The solvent further includes a low-boiling solvent composed of one or more solvent components having a boiling point of less than 200 ° C., and the proportion of the high-boiling solvent in the solvent is 80% or less. The manufacturing method of the organic light emitting element of description.  前記溶媒に占める前記高沸点溶媒の割合が60%以下である、請求項15に記載の有機発光素子の製造方法。 The method for producing an organic light-emitting element according to claim 15, wherein a ratio of the high boiling point solvent in the solvent is 60% or less.
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